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Physicochemical Aging Mechanisms in Soil Organic Matter (SOM- AGING): II. Hydration-dehydration mechanisms at Biogeochemical Interfaces

Soil organic matter (SOM) controls large part of the processes occurring at biogeochemical interfaces in soil and may contribute to sequestration of organic chemicals. Our central hypothesis is that sequestration of organic chemicals is driven by physicochemical SOM matrix aging. The underlying processes are the formation and disruption of intermolecular bridges of water molecules (WAMB) and of multivalent cations (CAB) between individual SOM segments or between SOM and minerals in close interaction with hydration and dehydration mechanisms. Understanding the role of these mediated interactions will shed new light on the processes controlling functioning and dynamics of biogeochemical interfaces (BGI). We will assess mobility of SOM structural elements and sorbed organic chemicals via advanced solid state NMR techniques and desorption kinetics and combine these with 1H-NMR-Relaxometry and advanced methods of thermal analysis including DSC, TGADSC- MS and AFM-nanothermal analysis. Via controlled heating/cooling cycles, moistening/drying cycles and targeted modification of SOM, reconstruction of our model hypotheses by computational chemistry (collaboration Gerzabek) and participation at two larger joint experiments within the SPP, we will establish the relation between SOM sequestration potential, SOM structural characteristics, hydration-dehydration mechanisms, biological activity and biogechemical functioning. This will link processes operative on the molecular scale to phenomena on higher scales.

Linking soil architecture formation with changing permafrost regime to carbon turnover in high latitude soils at multiple spatial scales

Most soils develop distinct soil architecture during pedogenesis and soil organic carbon (SOC) is sequestered within a hierarchical system of mineral-organic associations and aggregates. Permafrost soils store large amounts of carbon due to their permanently frozen subsoil and a lack of oxygen in the active layer, but they lack complex soil structure. With permafrost thaw more oxidative conditions and increasing soil temperature presumably enhance the build-up of more complex units of soil architecture and may counterbalance, at least partly, SOC mineralization. We aim to explore the development of mineral-organic associations and aggregates under different permafrost impact with respect to SOC stabilization. This information will be linked to environmental control factors relevant for SOC turnover at the pedon and stand scale to bridge processes occurring at the aggregate scale to larger spatial dimensions. We will combine in situ spectroscopic techniques with fractionation approaches and identify mechanisms relevant for SOC turnover at different scales by multivariate statistics and variogram analyses. From this we expect a deeper knowledge about soil architecture formation in the transition of permafrost soils to terrestrial soils and a scale-spanning mechanistic understanding of SOC cycling in permafrost regions.

Root distribution and dynamics and their contribution to subsoil C-fluxes

It has been suggested that dying and decaying fine roots and root exudation represent important, if not the most important, sources of soil organic carbon (SOC) in forest soils. This may be especially true for deep-reaching roots in the subsoil, but precise data to prove this assumption are lacking. This subproject (1) examines the distribution and abundance of fine roots (greater than 2 mm diameter) and coarse roots (greater than 2 mm) in the subsoil to 240 cm depth of the three subsoil observatories in a mature European beech (Fagus sylvatica) stand, (2) quantifies the turnover of beech fine roots by direct observation (mini-rhizotron approach), (3) measures the decomposition of dead fine root mass in different soil depths, and (4) quantifies root exudation and the N-uptake potential with novel techniques under in situ conditions with the aim (i) to quantify the C flux to the SOC pool upon root death in the subsoil, (ii) to obtain a quantitative estimate of root exudation in the subsoil, and (iii) to assess the uptake activity of fine roots in the subsoil as compared to roots in the topsoil. Key methods applied are (a) the microscopic distinction between live and dead fine root mass, (b) the estimation of fine and coarse root age by the 14C bomb approach and annual ring counting in roots, (c) the direct observation of the formation and disappearance of fine roots in rhizotron tubes by sequential root imaging (CI-600 system, CID) and the calculation of root turnover, (d) the measurement of root litter decomposition using litter bags under field and controlled laboratory conditions, (e) the estimation of root N-uptake capacity by exposing intact fine roots to 15NH4+ and 15NO3- solutions, and (f) the measurement of root exudation by exposing intact fine root branches to trap solutions in cuvettes in the field and analysing for carbohydrates and amino acids by HPLC and Py-FIMS (cooperation with Prof. A. Fischer, University of Trier). The obtained data will be analysed for differences in root abundance and activity between subsoil (100-200 cm) and topsoil (0-20 cm) and will be related to soil chemical and soil biological data collected by the partner projects that may control root turnover and exudation in the subsoil. In a supplementary study, fine root biomass distribution and root turnover will also be studied at the four additional beech sites for examining root-borne C fluxes in the subsoil of beech forests under contrasting soil conditions of different geological substrates (Triassic limestone and sandstone, Quaternary sand and loess deposits).

Diffusion and advection with sorption of anions, cations and non-polar molecules in organo-clays at varying thermo-chemical conditions - validation by analytical methods and molecular simulation

The sorption of anions in geotechnical multibarrier systems of planned high level waste repositories (HLWR) and of non-ionic and organic pollutants in conventional waste disposals are in the center of recent research. In aquatic systems, persistent radionuclides such as 79Se, 99Tc, 129I exist in a form of anions. There is strongly increasing need to find materials with high sorption capacities for such pollutants. Specific requirements on barrier materials are long-term stability of adsorbent under various conditions such as T > 100 C, varying hydrostatic pressure, and the presence of competing ions. Organo-clays are capable to sorb high amounts of cations, anions and non-polar molecules simultaneously having selectivity for certain ions. This project is proposed to improve the understanding of sorption and desorption processes in organo-clays. Additionally, the modification of material properties under varying chemical and thermal conditions will be determined by performing diffusion and advection experiments. Changes by sorption and diffusion will be analyzed by determining surface charge and contact angles. Molecular simulations on models of organo-clays will be conducted in an accord with experiments with aim to understand and analyze experimental results. The computational part of the project will profit from the collaboration of German partner with the group in Vienna, which has a long standing experience in a modeling of clay minerals.

Analysis of dairy production systems differentiated by location

Dairy farming across Germany displays diverse production systems. Factor endowment, management, technology adoption as well as competitive dynamics in the local or regional land, agribusiness and dairy processing sectors contribute to this differentiation on farm level. These differences impact on the ability of dairy farms and regional dairy production systems to successfully respond to pressures arising from future market and policy changes. The overall objective of the research activities of which this project is a part of, is to develop a thorough understanding of the processes that govern the spatial dynamics of dairy farm development in different regions in Germany. The central hypothesis of this research project is that management system and technological choices differ systematically across local production and market conditions. The empirical approach will focus on the estimation of farm specific nonparametric cost functions for dairy farms located in across Germany differentiated by time and location. A spatially differentiated data base with information on input use, resource availability, as well as local market conditions for land and output markets will be compiled. The nonparametric approach is specifically suited to disclose a more accurate representation of dairy production system heterogeneity across locations and time compared to parametric concepts as it provides the necessary flexibility to accommodate non-linearities relevant for a wide domain of explanatory variables. The methodology employed goes beyond the state of the art of the literature as it combines kernel density estimation with a Bayesian sampling approach to provide theory consistent parameters for each farm in the data sample.The specific methodological hypothesis is that the nonparametric approach is superior to current parametric techniques and this hypothesis is tested using statistical model evaluation. Regarding the farm management and technological choices, we hypothesize that land suitability for feed production determines the farm intensity of dairy production and thus management and technological choices. With respect to the ability of farms to successfully respond to market pressures we hypothesize that farms at the upper and lower tail of the intensity distribution both can generate positive returns from dairy production. These last two hypotheses will be tested using the estimated spatially differentiated farm specific costs and marginal costs.The expected outcomes are of relevance for the agricultural sector and the food supply chain economy as a whole as fundamental market structure changes in the dairy sector are ongoing due to the abolition of the quota regulation in the years 2014/2015. Thus, exact knowledge about differences and development of dairy cost heterogeneity of farms within and between regions are an important factor for the actors involved in the market as well as the political support of this process.

Natural variation of flowering time due to cis-regulatory evolution of FLOWERING LOCUS T and its orthologs and paralogs in Brassica napus

In many plant species, FLOWERING LOCUS T and related proteins are the mobile signal that communicates information on photoperiod from the leaves to the shoots, where the transition to flowering is realized. FT expression is tightly controlled at the transcriptional level so that it is restricted to leaves, occurs only in appropriate photoperiods, and integrates ambient temperature and developmental cues, as well as information on biotic and abiotic stress. We previously established that FT transcription in the model plant Arabidopsis thaliana requires proximal promoter cis-elements and a distal enhancer, both evolutionary conserved among Brassicacea species. In addition, FT transcription is blocked prior vernalization in biannual accessions and vernalization-dependency of FT is controlled through a CArG-box located in the first intron that binds the transcriptional repressor FLOWERING LOCUS C (FLC). Chromatin-mediated repression by the Polycomb Group (PcG) pathway is required for photoperiod-dependent FT regulation and participates in FT expression level modulation in response to other cues.In this project, I propose to explore the available sequence data from the 1001 genome project in Arabidopsis to evaluate how often changes in regulatory cis-elements at FT have occurred and how these translate into an adaptive value. Allele-specific FT expression pattern will be measured in F1 hybrids of different accessions in response to varying environmental conditions. FT alleles that show cis-regulatory variation will be further analyzed to pinpoint the causal regulatory changes and study their effect in more detail. The allotetrapolyploid species Brassica napus is a hybrid of two Brassiceae species belonging to the A- and C-type genome, which are in turn mesopolyploid due to a genome triplication that occurred ca. 10x106 years ago. We will determine allele-specific expression of FT paralogs from both genomes of a collection of B. napus accessions. The plants will be grown in the field in changing environmental conditions to maximize the chance to detect expression variation of the paralogs. We will compare the contribution of the founder genomes to the regulation of flowering time and asses variation in this contribution. A particular focus will be to study the impact of chromatin-mediated repression on allele selection in B. napus.

International Collaboration in Chemistry: First Principles Multi-Lattice Kinetic Monte Carlo Simulations of NOx Storage Reduction Catalysts

The broad objective of the research is to gain a fundamental understanding of the surface reaction chemistry of exhaust catalysts operating under cycling conditions. Using an integrated theoretical approach we specifically target NOx abatement, with particular emphasis on the appearance and destruction of surface oxide phases as the reactor conditions cycle from oxidative to reductive during the operation of the NOx Storage Reduction (NSR) catalyst system. Methodologically this requires material-specific, quantitative and explicitly time-dependent simulation tools that can follow the evolution of the system over the macroscopic time-scales of NSR cycles, while simultaneously accounting for the atomic-scale site heterogeneity and spatial distributions at the evolving surface. To meet these challenging demands we will develop a novel multi-scale methodology relying on a multi-lattice first-principles kinetic Monte Carlo (kMC) approach. As representative example the simulations will be carried out on a PdO(101)/Pd(100) surface oxide model, but care will be taken to ensure a generalization of the multi-lattice first-principles kMC approach to other systems in which phase transformations may occur and result in a change in the surface lattice structure depending upon environmental variables.

Nachbewilligung zur Dritten Phase des Projektes: Entwicklung eines zweistufigen biologischen Verfahrens zur Reinigung von Deponiesickerwasser und industriellen Abwässern mit komplexen Stoffgemischen

Zielsetzung und Anlass des Vorhabens: Ziel der letzten Projektphase war es, mit einer Langzeit-Praxiserprobung das zweistufige biologische Verfahren zur Deponiesickerwasserreinigung als Stand der Technik zu etablieren und zu bilanzieren. Nach der Inbetriebnahme des Technikums am Deponiestandort Schöneiche ging es in der zwölfmonatigen Laufzeit des Projektes AZ 14996/04 in den Langzeitversuchen um die Validierung der Laborergebnisse im technischen Maßstab, die verfahrenstechnische Optimierung der Anlage und um eine damit verbundene mögliche Kostenreduzierung des Systems. Darstellung der Arbeitsschritte und der angewandten Methoden: Nach dem ersten Technikums-Probebetrieb wurde eine Reihe von Optimierungsmaßnahmen durchgeführt: - der Umbau des Rohsickerwasserzulaufs, - die Verwendung von Soda statt Bicarbonat für die Ammoniumoxidation in Reaktor 2, - der Einsatz von Membrandosierpumpen mit integrierten Rückschlagventilen für die Zugabe von Soda und Essigsäure, - der Einbau von zusätzlichen Polyurethan-Festbetten zur Vergrößerung der Oberfläche für die Besiedlung mit Mikroorganismen, - die Einstellung des Sollwerts für Reaktor 4 auf einen pH-Wert von 6,5, - ein Update der SPS-Steuerung der Nanofiltration zur freien Programmierung der Spülzyklen, - der Einbau eines Absperrhahns vor den Nanofiltrations-Vorfilter - und die Trennung des Nanofiltrationsablaufs vom Reaktoren-Sammelablauf zur Behälterleerung. Es wurde sowohl Rohsickerwasser der MEAB-Deponie Schöneiche als auch Sickerwasserkonzentrat der Deponie Vorketzin behandelt. Fazit: Wegen der durchgeführten Optimierungsmaßnahmen ist es prinzipiell gelungen, das Schöneicher Rohsickerwasser gemäß Anhang 51 der Abwasserverordnung aufzureinigen. In Vorketzin wurde die organische Belastung über 70% und Stickstoff über 80% reduziert. Nach Rückgang der Calciumfracht sollte es zukünftig möglich sein, mit der Zweistufen-Biologie das Sickerwasserkonzentrat ausreichend zu reinigen, da organische Belastung und Stickstoffgehalt geringer als im Schöneicher Rohsickerwasser sind. Um das Verfahren als Stand der Technik, vor allem für die Behandlung von Sickerwasserkonzentraten, zu etablieren, müssten die Laborvorgaben mit den Erfahrungen des Technikumsbetriebs kombiniert und in einer weiteren Versuchsreihe unter optimierten Bedingungen verifiziert werden.

The scalar organization of environmental governance: an institutionalist perspective on the transformation of water and marine governance in the European Union

The project aims to theorize the scalar organization of natural resource governance in the European Union. This research agenda is inspired by critical geographers' work on the politics of scale. The research will examine an analytical framework derived from theories of institutional change and multi-level govern-ance to fill this theoretical gap. Furthermore, it will review conceptualizations of the state in institutional economics, evaluate their adequacy to capture the role of the state in the dynamics identified, and develop them further. The described processes may imply shifts in administrative levels, shifts in relations between different levels and changes in spatial delimitations of competent jurisdictions that result, for example, from decentralization or the introduction of river basin oriented administrative structures. The research investigates the implications of two European Directives: the Water Framework Directive (WFD) and the Marine Strategy Framework Directive (MSFD). They both have potentially great significance for the organization of marine and water governance at the level of Member States and below, and adhere to similar regulatory ideas for achieving good ecological status of waters. A multiple case study on changes in the scalar reorganization of marine and water governance that result from the implementation of the Directives will be carried out. It will rely on qualitative and quantitative data gathering based on semi-structured interviews and review of secondary and tertiary sources looking at Portugal, Spain, and Germany. It specifically addresses the role of social ecological transactions, the structure of decision making processes and the role of changes in contextual factors (such as ideologies, interdependent institutions and technology).

Release of hexavalent chromium from ore processing residues and the potential of biochar for chromium immobilization in polluted soils

Chromium (Cr) is introduced into the environment by several anthropogenic activities. A striking ex-ample is the area around Kanpur in the Indian state of Uttar Pradesh, where large amounts of Cr-containing wastes have been recently illegally deposited. Hexavalent Cr, a highly toxic and mobile contaminant, is present in significant amounts in these wastes, severely affecting the quality of sur-roundings soils, sediments, and ground waters. The first major goal of this study is to clarify the solid phase speciation of Cr in these wastes and to examine its leaching behavior. X-ray diffraction and synchrotron-based X-ray absorption spectroscopy techniques will be employed for quantitative solid phase speciation of Cr. Its leaching behavior will be studied in column experiments performed at un-saturated moisture conditions with flow interruptions simulating monsoon rain events. Combined with geochemical modeling, the results will allow the evaluation of the leaching potential and release kinetics of Cr from the waste materials. The second major goal is to investigate the spatial distribution, speciation, and solubility of Cr in the rooting zone of chromate-contaminated soils surrounding the landfills, and to study the suitability of biochar as novel soil amendment for mitigating the deleterious effects of chromate pollution. Detailed field samplings and laboratory soil incubation studies will be carried out with two agricultural soils and biochar from the Kanpur region.

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